KR100854071B1 - Apparatus for removal of odor gas from pig pen and hen house by using mediated electrochemical oxidation - Google Patents

Apparatus for removal of odor gas from pig pen and hen house by using mediated electrochemical oxidation Download PDF

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KR100854071B1
KR100854071B1 KR1020070023227A KR20070023227A KR100854071B1 KR 100854071 B1 KR100854071 B1 KR 100854071B1 KR 1020070023227 A KR1020070023227 A KR 1020070023227A KR 20070023227 A KR20070023227 A KR 20070023227A KR 100854071 B1 KR100854071 B1 KR 100854071B1
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gas
mediated
scrubber
liquid contact
oxidation
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Korean (ko)
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문일식
정상준
강문식
장병석
최태원
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(주) 파루
문일식
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/32—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00
    • B01D53/326—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00 in electrochemical cells
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/52—Hydrogen sulfide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/54—Nitrogen compounds
    • B01D53/58—Ammonia
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77—Liquid phase processes
    • B01D53/78—Liquid phase processes with gas-liquid contact
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/304—Hydrogen sulfide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/306—Organic sulfur compounds, e.g. mercaptans
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B01D2257/406—Ammonia

Abstract

An apparatus for the removal of odorous gases by mediated electrochemical oxidation is provided to remove consistently the odorous gases at a high removal efficiency by increasing the oxidation efficiency of the odorous gases, and reduce initial investment cost of the apparatus and operate the apparatus easily by simplifying the apparatus. An apparatus for the removal of odorous gases by mediated electrochemical oxidation comprises: a gas-liquid contact mediated oxidation scrubber(10) filled with a filler for mediated oxidation of an odorous gas mixture by mediation ions; a mediation ion introduction pipe(11) connected to an upper part of the gas-liquid contact mediated oxidation scrubber to spray mediation ions produced in an anode chamber of an electrolysis cell(40); an odorous gas introduction pipe(12) for introducing an odorous gas mixture from a lower part of the gas-liquid contact mediated oxidation scrubber; an anolyte storage tank(20) for storing an anolyte through a recovery pipe(14) and injecting the anolyte into an anode chamber of an electrolysis cell, wherein the recovery pipe recovers mediation ions reduced by contacting the mediation ions with the odorous gases from the gas-liquid contact mediated oxidation scrubber; a catholyte storage tank(50) for adjusting a mass balance with the anolyte storage tank; and an electrostatic precipitator or a heat exchanger(70) which is connected to a decomposed gas exhaust pipe(13) formed on a top part of the gas-liquid contact mediated oxidation scrubber, and which collects water, mediation metal ions, or nitric acid from the gas-liquid contact mediated oxidation scrubber to recover the collected water, mediation metal ions, or nitric acid into the anolyte storage tank. Further, the odorous gas is ammonia, H2S, CH3SH or a mixture thereof.

Description

전기화학적 매개산화를 이용한 돈사, 계사에서 발생되는 악취가스 처리장치{Apparatus for removal of odor gas from pig pen and hen house by using mediated electrochemical oxidation}Apparatus for removal of odor gas from pig pen and hen house by using mediated electrochemical oxidation}

도 1은 본 발명에 따른 악취가스매개산화공정의 개념도이고,1 is a conceptual diagram of a malodorous gas medium oxidation process according to the present invention,

도 2는 본 발명에 따른 악취가스매개산화공정의 장치 구성도이고,2 is a block diagram of the odor gas mediated oxidation process according to the present invention,

도 3은 본 발명의 실시예 1에 따른 NH3 제거 결과를 나타낸 그래프이고,3 is a graph showing a result of NH 3 removal according to Example 1 of the present invention,

도 4는 본 발명의 실시예 2에 따른 H2S 제거 결과를 나타낸 그래프이고,4 is a graph showing the result of removing H 2 S according to Example 2 of the present invention;

도 5는 본 발명의 실시예 3에 따른 H2S 제거 결과를 나타낸 그래프이고,5 is a graph showing the result of removing H 2 S according to Example 3 of the present invention;

도 6은 본 발명의 실시예 4에 따른 CH3SH 제거 결과를 나타낸 그래프이며,6 is a graph showing the results of CH 3 SH removal according to Example 4 of the present invention,

도 7은 본 발명의 실시예 4에서 CH3SH 제거에 따른 CO2 발생 결과를 나타낸 그래프이다.7 is a graph showing the results of CO 2 generation according to the CH 3 SH removal in Example 4 of the present invention.

*도면의 주요부분에 대한 부호의 설명** Description of the symbols for the main parts of the drawings *

10 : 기-액접촉매개산화스크러버 11 : 매개이온도입관10: gas-liquid contact mediated oxidation scrubber 11: medium temperature entrance

12 : 악취가스도입관 13 : 분해가스배출관12: odor gas introduction pipe 13: cracked gas discharge pipe

14 : 회수관 20 : 아노드액(anolyte)저장조 14: recovery tube 20: anolyte storage tank

30 : 정류기 40 : 전해셀 30: rectifier 40: electrolytic cell

41 : 아노드실 42 : 캐소드실41: anode chamber 42: cathode chamber

43 : 전해격막 50 : 캐소드액(catholyte)저장조43: electrolytic diaphragm 50: catholyte storage tank

60 : MFC(Mas Flow Controller) 70 : 열교환기60: MFC (Mas Flow Controller) 70: heat exchanger

본 발명은 전기화학적 매개산화에 의한 악취가스 처리장치에 관한 것이다.The present invention relates to a malodorous gas treatment apparatus by electrochemical mediated oxidation.

돈사나 계사와 같은 축산시설에서 발생하는 악취가스 중에는 황화수소(H2S), 메틸메르캅탄(CH3SH), 이황화메틸((CH3)2S2) 등의 유황계 화합물과 암모니아(NH3), 아민류((CH3)3N) 등의 암모니아계, 그리고 아세트산(acetic acid), 프로피온산(propionic acid), 발레르산(valeric acid) 등의 저급지방산이 포함되어 있으나, 주요 악취유발 물질로는 H2S, CH3SH, 암모니아가 알려져 있다. Odor gases from livestock facilities such as pig and poultry houses include sulfur compounds such as hydrogen sulfide (H 2 S), methyl mercaptan (CH 3 SH) and methyl disulfide ((CH 3 ) 2 S 2 ) and ammonia (NH 3). ), Ammonia such as amines ((CH 3 ) 3 N), and lower fatty acids such as acetic acid, propionic acid, valeric acid, etc. H 2 S, CH 3 SH, ammonia are known.

이러한 법 등이 시도되어 왔으며, 최근에는 바이오필터를 이용한 처리방식이 관심있게 악취의 제거방법으로는 냉각응축, 고온산화(열소각), 촉매산화, 흡착, 생물학적 처리진행되고 있다.Such methods have been attempted, and recently, the treatment method using a biofilter has been interested, and as a method of removing odors, cooling condensation, high temperature oxidation (heat incineration), catalytic oxidation, adsorption, and biological treatment have been performed.

냉각응축법은 고농도의 악취물질 제거에는 경제성 면에서 시설비와 운영비가 많이 드는 단점이 있으며, 흡착법도 흡착제의 최종처리 및 교체로 인해 비경제적인 단점이 있다. 촉매산화법은 경제성은 있으나 촉매산화 시 납, 비소, 황 안티몬, 수은, 아연, 철산화물 또는 다른 촉매유도체를 포함하는 배출가스가 촉매의 활성을 급격히 저하시키므로 전처리 과정을 거쳐야 하는 등 문제점이 따른다. The cooling condensation method has a disadvantage in that it is economically expensive to remove odorous substances at a high concentration, and the adsorption method is also uneconomical due to the final treatment and replacement of the adsorbent. Catalytic oxidation is economical, but exhaust gas containing lead, arsenic, antimony sulfur, mercury, zinc, iron oxide, or other catalyst derivatives rapidly reduces the activity of the catalyst, and thus requires pretreatment.

생물학적 처리기술은 혼합미생물군의 화학물질 분해능력을 이용하여 악취물질을 제거하는 기술로서 악취분해 미생물을 직접 사료에 첨가하는 생균첨가제나 충전재의 입자표면에 정착한 미생물에 의하여 악취성분을 분해시키는 생물막 탈취장치에 관심이 집중되고 있다. 그러나 생물학적 악취물질 처리기술에서 중요 사항인 미생물의 지속적 투입 및 유지관리와 미생물 생활환경의 조성 등이 양축농가에서 유지되기는 어려움 점이 많다. Biological treatment technology is a technology that removes odorous substances by using chemical decomposition ability of mixed microorganisms. Biofilm that decomposes odorous substances by bioadditives that directly add odorous microorganisms to feed or microorganisms settled on the particle surface of filler. Attention is focused on deodorizers. However, it is difficult to maintain continuous input and maintenance of microorganisms and the creation of microbial living environment, which are important in biological malodorous substance treatment technology, in farms.

갈수록 악화되고 있는 국내 환경오염문제의 해결은 물론, 대외적인 환경규제가 점점 강화되고 있는 시점에서, 기존 악취물질 처리기술을 대처할 수 있으며, 국내 축사(돈사 및 계사) 시설, 음식물처리장 및 산업시설 등에서 유지 및 운전이 쉬우며 높은 악취물질 제거효율을 가진 경쟁력 있는 새로운 환경기술의 개발이 필요한 시기라 판단된다.In addition to solving domestic environmental pollution problems that are getting worse and worsening, external environmental regulations are being strengthened, and existing odorous substance treatment technologies can be coped with. It is time to develop new environmental technologies that are easy to maintain and operate and have high odor removal efficiency.

상기와 같은 문제점을 해결하기 위해서, 본 발명은 전기화학적 매개산화방식을 통하여 매개산화공정 중 환원된 매개이온을 산화시키는 반응을 수행하는 동시에 산화된 매개이온을 이용하여 기-액접촉시키는 장치를 개발함으로써, 그 동안 개발되지 못하였던, 매개산화방식을 이용한 기-액접촉식 악취가스 제거장치를 발명하게 되었다. In order to solve the above problems, the present invention develops an apparatus for performing gas-liquid contact using the oxidized mediated ions while performing a reaction for oxidizing the reduced mediated ions during the mediated oxidation process through an electrochemical mediated oxidation method. As a result, the gas-liquid odor gas removal device using the mediated oxidation method, which has not been developed in the past, has been invented.

본 발명은 일체형 기-액접촉 매개산화스크러버에서 기-액 접촉을 시행함으로써 악취가스의 산화효율을 증가시키고 악취가스를 높은 처리효율로 지속적으로 처리할 수 있으며, 장치가 간단하고, 협소한 장소에서도 설치가능하고 제거 효율이 우수하여 초기 장치 투자비와 운전의 용이성이 있는 환경친화적인 처리장치 및 방법을 제공하는데 목적이 있다.The present invention can increase the oxidation efficiency of odor gas and continuously process the odor gas with high processing efficiency by performing gas-liquid contact in the integrated gas-liquid contact mediated oxidation scrubber, the device is simple, even in a narrow place It is an object of the present invention to provide an environmentally friendly treatment apparatus and method which is easy to install and has an excellent removal efficiency, which makes initial equipment investment cost and ease of operation.

본 발명은 전기화학적 매개산화에 의한 악취가스 처리장치에 관한 것으로서,구체적으로는 금속이온을 매개체로 이용하는 매개 전기화학적 산화(Mediated Electrochemical Oxidation, MEO) 공정을 이용하여 돈·양계 시설에서 발생되는 암모니아, H2S, CH3SH 등과 같은 악취물질을 효과적으로 처리할 수 있는 처리 장치를 제공한다. The present invention relates to an apparatus for treating malodorous gas by electrochemical mediated oxidation, specifically, ammonia generated in pig and poultry facilities using a mediated electrochemical oxidation (MEO) process using metal ions as a mediator, Provided is a treatment apparatus capable of effectively treating malodorous substances such as H 2 S and CH 3 SH.

본 발명은 유입된 악취가스혼합물이 매개이온에 의하여 매개산화되는 충진재로 충진된 기-액접촉매개산화스크러버, 상기 기-액접촉매개산화스크러버의 상부에 연결되고 전해셀의 아노드실에서 생성되는 매개이온을 분사하는 매개이온도입관, 상기 기-액접촉매개산화스크러버의 하단부에서 악취가스혼합물을 도입하는 악취가스도입관을 포함하고, 상기 악취가스도입관으로부터 도입되는 악취가스혼합물이 기-액접촉매개산화스크러버에서 매개이온과 접촉 반응하여 악취가스를 산화시켜 제거 하는 것을 특징으로 하는 전기화학적 매개산화 악취가스 처리장치를 제공한다.The present invention is a gas-liquid contact mediated scrubber filled with a filler that is oxidized gas mixture by the mediated ions, connected to the upper portion of the gas-liquid contact mediated oxidation scrubber and generated in the anode chamber of the electrolysis cell Mediated temperature inlet pipe for injecting ions, malodorous gas introduction pipe for introducing a malodorous gas mixture at the lower end of the gas-liquid contact mediated oxidation scrubber, the malodorous gas mixture introduced from the malodorous gas introduction pipe is a gas-liquid contact medium Provided is an electrochemical mediated odor gas treatment apparatus, characterized in that the odor gas is oxidized and removed by contacting with medium ions in an oxidation scrubber.

상기 매개이온은 Ce3+, Ag+, Co2+ 또는 Mn2+인 것이 바람직하고, 세륨이온(Ce3+) 또는 은이온(Ag+)인 것이 보다 바람직하다.The intermediate ion is preferably Ce 3+ , Ag + , Co 2+ or Mn 2+ , and more preferably cerium ion (Ce 3+ ) or silver ion (Ag + ).

본 발명에 따른 악취가스 처리장치의 상기 기-액접촉매개산화스크러버의 상부에는 분해가스배출관을 구비하고 하부에는 환원된 금속을 회수하는 회수관을 더 구비할 수 있다. 또한, 상기 분해가스배출관은 기-액접촉매개산화스크러버로부터 배출되는 수분, 매개 금속이온 또는 질산의 손실을 막기 위해 열교환기 또는 전기집진기와 연결되는 것이 바람직하다. In the upper portion of the gas-liquid contact medium oxidation scrubber of the malodor gas treatment apparatus according to the present invention may be provided with a decomposition gas discharge pipe and a lower recovery pipe for recovering the reduced metal. In addition, the decomposition gas discharge pipe is preferably connected to a heat exchanger or electrostatic precipitator to prevent the loss of moisture, mediated metal ions or nitric acid discharged from the gas-liquid contact mediated oxidation scrubber.

또한, 본 발명에 따른 악취가스 처리장치의 상기 전해셀은 아노드실, 케소드실 및 전해격막으로 구성되고, 정류기에 의해 전류가 공급되어 환원된 매개이온을 산화하는 기능을 하며, 기-액접촉매개산화스크러버 하부의 회수관으로부터 유입되는 환원된 매개이온이 전해셀에서 산화되어 매개이온도입관을 통해 기-액접촉매개산화스크러버 상부로 주입된다.In addition, the electrolytic cell of the malodor gas treatment apparatus according to the present invention is composed of an anode chamber, a cathode chamber and an electrolytic diaphragm, and serves to oxidize the reduced mediated ion by supplying a current by a rectifier, and gas-liquid contact. The reduced mediated ions flowing from the recovery tube under the mediated oxidation scrubber are oxidized in the electrolytic cell and injected into the upper part of the gas-liquid contact mediated oxidation scrubber through the mediated temperature inlet tube.

또한, 본 발명에 따른 악취가스 처리장치의 상기 기-액접촉매개산화스크러버 충진재는 매개산화이온의 강력한 산화력에 내성을 갖는 테프론 재질의 충진재인 것이 바람직하고, 또한, 상기 악취가스도입관은 악취가스유량을 조절하는 MFC와 연결되어 있는 것이 바람직하다.In addition, the gas-liquid contact mediated oxidation scrubber filler of the malodorous gas treating apparatus according to the present invention is preferably a filler made of Teflon material resistant to the strong oxidizing power of the mediated oxidation ion, the malodorous gas introduction pipe is a malodorous gas It is desirable to be connected to the MFC to control the flow rate.

본 발명에 따른 악취가스 제거 장치는 기존의 돈사, 계사에서 발생되는 악취물질 제거에 적용되는 기술 또는 연구되고 있는 기술과는 근본적으로 달리, 강력한 산화력을 가진 매개 금속이온(Ce, Ag, Mn 등)을 이용하여 악취가스를 처리할 수 있는 기술로서, 산성 전해질 용액에 용해되어 있는 매개 금속이온을 전기화학적인 방법에 의해 산화시켜 산화된 매개 금속이온이 가진 강력한 산화력을 이용하여 악취가스를 무해한 물질로 완전 분해 처리하는 기술이다.The odor gas removal device according to the present invention is fundamentally different from the technology applied to the removal of odorous substances generated in pigs, cages, or the researched technology, mediated metal ions (Ce, Ag, Mn, etc.) having strong oxidizing power. It is a technology that can deal with odor gas by using oxidization method. The odor gas is converted into harmless substance by using the strong oxidizing power of oxidized intermediate metal ion by oxidizing the mediated metal ion dissolved in acid electrolyte solution by electrochemical method. It is a technology that completely disintegrates.

본 발명에 따른 악취가스 제거장치에서 H2S, CH3SH, NH3와 같은 악취가스는 산화된 매개이온(Mn+1)에 의해 CO2와 H2O로 완전 산화 처리됨과 동시에 산성 전해질 용액에 흡수되어 처리된다. 이때 악취가스 처리반응에 사용되고 환원된 매개이온(Mn)은 전해셀에서 산화된 매개이온(Mn+1)으로 연속적으로 재생되어 사용된다. 따라서 추가적인 매개이온 및 전해질의 공급 없이 전력공급에 의해서만 지속적으로 산화와 환원을 반복해가면서 악취가스를 지속적으로 청정처리 할 수 있는 차세대 청정처리 기술이다. 또한 기존의 냉각응축, 고온산화(열소각), 촉매산화, 흡착, 생물학적 처리법 등의 기술과 달리 여러 가스의 동시 처리가 가능하고, 높은 처리효율을 얻을 수 있을 뿐 아니라 사용된 촉매와 흡착제, 흡수제의 교체 및 2차 오염물질의 배출이 없어 저비용 고효율의 지속적인 처리가 가능하다.In the malodorous gas removing apparatus according to the present invention, the malodorous gases such as H 2 S, CH 3 SH, and NH 3 are completely oxidized to CO 2 and H 2 O by an oxidized mediated ion (M n + 1 ) and an acidic electrolyte. Absorbed in solution and processed. In this case, the odor gas treatment reaction is used and the reduced mediated ions (M n ) are continuously recycled to the oxidized mediated ions (M n + 1 ) in the electrolytic cell. Therefore, it is a next-generation clean processing technology that can continuously clean the odorous gas while repeating oxidation and reduction only by power supply without supplying additional intermediate ions and electrolytes. Unlike conventional cooling condensation, high temperature oxidation (heat incineration), catalytic oxidation, adsorption, and biological treatment methods, it is possible to process several gases simultaneously and obtain high treatment efficiency, as well as used catalysts, adsorbents and absorbents. It is possible to maintain low cost and high efficiency since there is no replacement and no emission of secondary pollutants.

이하, 도면을 참조하여 본 발명을 상세히 설명한다. Hereinafter, the present invention will be described in detail with reference to the drawings.

도 1은 매개이온으로 Ce(Ⅳ)과 Ag(Ⅱ)를 이용하는 전기화학적 매개산화 공정의 개념도이고, 도 2는 전기화학적 매개산화(Mediated Electrochemical Oxidation, MEO)를 이용한 악취가스 처리 장치를 나타낸 것이다.1 is a conceptual diagram of an electrochemical mediated oxidation process using Ce (IV) and Ag (II) as mediator ions, and FIG. 2 illustrates an odor gas treatment apparatus using mediated electrochemical oxidation (MEO).

도 1을 참조하면, MEO 공정을 이용한 악취물질 제거 기술은 악취가스를 매개 금속이온에 의해 직접 산화시켜 완전 분해하거나, 산화와 동시에 전해용액에 흡수 시켜 처리할 수 있는 획기적인 기술이다. 또한, 악취가스 처리에 사용되는 매개금속이온은 전해용액과 함께 전해셀에서 연속적으로 산화재생 됨으로써 반복 사용할 수 있어 매개금속이온과 전해용액을 보충 및 교환할 필요가 없다. 따라서 본 기술은 처리공정 중 슬러지 혹은 폐 산화제등에 의한 2차 오염물의 배출 없이 전력의 공급에 의해서만 운전할 수 있는 지속가능한 악취가스 청정처리기술이다.Referring to FIG. 1, the odor substance removal technology using the MEO process is a breakthrough technology that can directly oxidize odor gas by mediating metal ions to completely decompose or absorb and treat the odor gas at the same time as the oxidation. In addition, the medial metal ions used in the odor gas treatment can be repeatedly used in the electrolysis cell together with the electrolyte solution, so that it is not necessary to replenish and exchange the medial metal ion and the electrolyte solution. Therefore, this technology is a sustainable odor gas clean treatment technology that can be operated only by supplying electric power without discharging secondary pollutants by sludge or waste oxidant during the treatment process.

도 2를 참조하면, 본 발명에 따른 악취가스 처리장치는 정류기(30)로부터의 전류에 의하여 상기 기-액접촉매개산화스크러버(10)로부터 유입되는 환원된 매개이온이 산화되는 아노드실(41), 아노드실(41)로부터 전자를 받아 캐소드액을 환원시키는 캐소드실(42) 및 상기 아노드실(41)과 캐소드실(42)의 사이에 전해격막(43)이 구비된 전해셀(40); 상기 아노드실(41)에서 산화된 매개이온이 도입되는 기-액접촉매개산화스크러버(10)의 상부에 연결된 매개이온도입관(11)과 스크러버 하부에 연결된 악취가스도입관(12) 및 스크러버 상부에 외부와 연결된 분해가스배출관(13); 상기 분해가스배출관(13)과 연결되어 스크러버(10)로부터 배출되는 가스로 인해 수분, 매개 금속이온 또는 질산의 손실을 막기 위해 스크러버 상부에 열교환기(70) 또는 전기집진기(미도시)로 구성되며, 악취가스도입관(12)과 연결되어 악취가스 유량을 조절하는 MFC(60)를 구비할 수도 있다. 또한 스크러버(10) 하부에 설치되어 악취가스와 접촉에 의해 환원된 매개이온을 회수하는 회수관(14)을 통하여 아노드액(anolyte)를 저장하는 아노드액저장조(20)으로 구성되며, 아노드액저장조(20)와 물질균형을 맞추기 위하여 설치한 캐소드액(catholyte)저장조(50)로 구성된다.Referring to FIG. 2, in the odor gas treatment apparatus according to the present invention, an anode chamber 41 in which reduced mediated ions introduced from the gas-liquid contact mediated oxidation scrubber 10 are oxidized by a current from the rectifier 30. A cathode chamber 42 which receives electrons from the anode chamber 41 and reduces cathode liquid; and an electrolysis cell 40 provided with an electrolytic separator 43 between the anode chamber 41 and the cathode chamber 42; The intermediate temperature inlet pipe 11 connected to the upper portion of the gas-liquid contact mediated oxidation scrubber 10 into which the oxidized medium ion is introduced in the anode chamber 41 and the odor gas introduction pipe 12 connected to the lower portion of the scrubber and the upper portion of the scrubber Decomposition gas discharge pipe 13 connected to the outside; Is connected to the decomposition gas discharge pipe 13 is composed of a heat exchanger 70 or an electrostatic precipitator (not shown) on the top of the scrubber to prevent the loss of water, medial metal ions or nitric acid due to the gas discharged from the scrubber 10 In addition, it may be provided with the MFC (60) connected to the odor gas introduction pipe 12 to adjust the odor gas flow rate. It is also composed of an anode liquid storage tank (20) for storing the anolyte (anolyte) through the recovery pipe 14 is installed in the lower portion of the scrubber (10) to recover the mediated ions reduced by contact with the malodorous gas, It consists of a catholyte storage tank (50) installed in order to balance the material and the node liquid storage tank (20).

도 2에 예시한 악취가스 처리 장치를 이용한 악취가스 처리방법에 대하여 설명한다. The odor gas treatment method using the odor gas treatment device illustrated in FIG. 2 will be described.

악취가스를 악취가스도입관(12)을 통하여 MFC(Mass Flow Controller)(60)를 이용하여 유속을 제어하여 일정 농도로 또는 일정한 농도로 희석된 악취가스를 기-액접촉매개산화스크러버(10)에 공급한다.The odor gas is controlled by the MFC (Mass Flow Controller) 60 through the odor gas introduction pipe 12 to control the flow rate of the odor gas diluted to a predetermined concentration or to a constant concentration in the gas-liquid contact medium oxidation scrubber 10. To feed.

매개금속이온으로 사용된 Ce과 Ag는 악취가스 분해를 위한 스크러버(10)에 도입되기 전에 전해격막(43)으로서 예를들면 나피온(Nafion) 324에 의해 캐소드실(42)과 아노드실(41)이 분리된 전해셀(40)에 전류를 공급함으로써 Ce(IV) 및 Ag(II)로 산화시킨 후, 악취가스가 스크러버(10)에서 처리되는 동안에도 전해셀(40)에 계속 전류를 공급하여 악취가스 산화분해에 의해 Ce(III)와 Ag(I)으로 환원된 매개 금속이온을 연속적으로 산화시키면서 Ce(IV)와 Ag(II)에 의한 악취가스의 분해가 진행될 수 있도록 한다.Ce and Ag, used as intermediate metal ions, are introduced to the scrubber 10 for decomposition of odor gas, and are formed by the cathode chamber 42 and the anode chamber, for example, by Nafion 324 as an electrolytic diaphragm 43. ) Is oxidized to Ce (IV) and Ag (II) by supplying a current to the separated electrolytic cell 40 and then continues to supply current to the electrolytic cell 40 even while the malodorous gas is processed in the scrubber 10. By oxidizing the odor gas by oxidative decomposition of Ce (III) and Ag (I) mediated metal ions are continuously oxidized to allow the decomposition of the odor gas by Ce (IV) and Ag (II).

이때 스크러버(10)의 사이즈는 필요에 의해 조절가능한 것이며, 예를 들면, 내경은 φ10cm이고, 높이는 90cm이며, Ag(II) 및 Ce(IV)가 포함된 아노드액(anolyte)에 의해 악취가스가 분해되는 실제구간은 충진재(packing material)가 충진되어 있는 높이 60cm내에서 가스와 아노드액(Anolyte)이 상부에서 분사되어 접촉하여 분해처리 되도록 한다. 스크러버(10) 내의 충진제는 Ce(IV)와 Ag(II) 및 질산 전해질에 의해 쉽게 분해되지 않으며 내산성 및 내구성이 강한 물질이라면 어떤 형태이고 어떤 것이든 크게 관련이 없지만, 예를 들면 테프론(teflon) 계열의 충진 재(Tri-Pack, PFA, Jaeger Products iNC.)를 충진하여 악취혼합가스와 Ce(IV) 및 Ag(II)이 포함된 전해질과의 접촉을 이루어 악취가스 혼합물을 처리할 수 있으며, 상기 재질의 경우 보다 내구성이 강하여 보다 추천된다.At this time, the size of the scrubber 10 is adjustable as necessary, for example, the inner diameter is 10cm, the height is 90cm, odor gas by the anolyte containing Ag (II) and Ce (IV) The actual section is decomposed so that the gas and anode liquid (Anolyte) is sprayed from the upper side within 60cm of the height of the packing material (filling material) is filled in contact with the decomposition process. The fillers in the scrubber 10 are not easily decomposed by Ce (IV), Ag (II) and nitric acid electrolytes and are of any form and are not strongly related to any acid resistant and durable material, but are not related to, for example, teflon. By filling a series of fillers (Tri-Pack, PFA, Jaeger Products iNC.), The malodorous gas mixture can be contacted with an electrolyte containing Ce (IV) and Ag (II) to treat the malodorous gas mixture. In the case of the material is more durable than the recommended.

또한 스크러버(10)의 상부로 부터 도입되는 악취가스 혼합물중 악취가스로서 황화수소(H2S), 메틸메르캅탄(CH3SH), 이황화메틸((CH3)2S2), 암모니아(NH3)등의 악취물질은 분해처리되지만, 스크러버에 도입되는 가스 중 대부분을 차지하는 공기와 N2 등은 스크러버 밖으로 그대로 배출된다. 이 때 스크러버로부터 배출되는 가스 중에는 스크러버에 도입되는 가스의 유속에 의해 수분, 매개 금속이온 또는 질산이 배출될 수 있고, 또한 스크러버 내 아노드액(anolyte)의 온도에 의해 수분, 매개 금속이온 또는 질산이 증발되어 스크러버 밖으로 배출될 수 있는데, 이렇게 스크러버로부터 수분, 매개 금속이온 또는 질산이 증발되어 배출된다면 악취가스 혼합물을 처리하기 위한 초기 아노드액(Anolyte)의 조건이 반응시간이 지남에 따라 계속 달라질 것이며, 손실되는 매개 금속이온과 전해질로 인해 악취가스의 처리효율 감소될 수 있다. 따라서 스크러버(10)로부터 배출되는 가스로 인해 수분, 매개 금속이온 또는 질산의 손실을 막기 위해 스크러버 상부에 열교환기(70) 또는 전기집진기를 연결하여 증발되는 수분, 매개 금속이온 또는 질산을 포집하여 다시 아노드액저장조(20)로 회수함으로써 아노드액(Anolyte)의 초기 조건을 계속 유지하고, 악취가스 혼합물을 높은 처리효율로 지속적으로 처리한다.In addition, as a malodorous gas in the malodorous gas mixture introduced from the upper portion of the scrubber 10, hydrogen sulfide (H 2 S), methyl mercaptan (CH 3 SH), methyl disulfide ((CH 3 ) 2 S 2 ), ammonia (NH 3 Odor substances such as) are decomposed, but air and N 2 , which occupy most of the gas introduced into the scrubber, are discharged out of the scrubber. At this time, in the gas discharged from the scrubber, water, medial metal ions or nitric acid may be discharged by the flow rate of the gas introduced into the scrubber, and moisture, medial metal ions or nitric acid may be discharged by the temperature of the anolyte in the scrubber. This can be evaporated and discharged out of the scrubber. If moisture, mediated metal ions or nitric acid are evaporated and released from the scrubber, the conditions of the initial anolyte for treating the malodorous gas mixture will continue to change over time. Due to the loss of the mediated metal ions and the electrolyte, the treatment efficiency of the malodorous gas may be reduced. Therefore, in order to prevent the loss of moisture, medial metal ions or nitric acid due to the gas discharged from the scrubber 10, the heat exchanger 70 or an electrostatic precipitator is connected to the scrubber to collect and evaporate moisture, medial metal ions or nitric acid. By recovering to the anolyte storage tank 20, the initial conditions of the anolyte are maintained continuously, and the malodorous gas mixture is continuously treated with high processing efficiency.

본 발명에 따른 악취가스 처리장치에서 매개이온으로는 전이금속 이온이 적 절하며, 특히 Ce3+, Ag+, Co2+, Mn2+으로부터 선택되는 1종 이상이 바람직하고, 산화력 면이나 공정의 운용면에서 Ce3+, Ag+이 더 바람직하다. 상기 매개 이온은 질산 또는 황산 수용액 상에 용해되어 기-액접촉매개산화스크러버(10)에서 악취가스를 매개산화반응에 의하여 산화시키고 자신은 환원된 후에 전해셀(40)의 아노드실(41)에서 전기화학적 방법으로 산화되어 다시 순환되는 과정을 거치며, 매개이온의 농도는 0.5M 내지 1.6M이며, 바람직하기는 0.8M 내지 1.5M이다.In the malodorous gas treatment apparatus according to the present invention, the transition metal ion is appropriate as the medium ion, and at least one selected from Ce 3+ , Ag + , Co 2+ , and Mn 2+ is preferable, and the oxidation power or process Ce 3+ , Ag + is more preferable in terms of operation. The intermediate ions are dissolved in an aqueous solution of nitric acid or sulfuric acid to oxidize the malodorous gas by a mediated oxidation reaction in the gas-liquid contact mediated oxidation scrubber 10, and then reduce itself in the anode chamber 41 of the electrolytic cell 40. Oxidized and circulated again by an electrochemical method, the concentration of the mediated ion is 0.5M to 1.6M, preferably 0.8M to 1.5M.

또한, 상기 전해셀(40)의 캐소드실(42)에서는 아노드실(41)에서의 매개이온의 산화와 동시에 캐소드액(catholyte)이 환원되게 되며, 상기 캐소드액은 HNO3 또는 H2SO4 수용액이 바람직하다.In addition, in the cathode chamber 42 of the electrolytic cell 40, the catholyte is reduced at the same time as the oxidation of the medium ion in the anode chamber 41, and the catholyte solution is HNO 3 or H 2 SO 4 aqueous solution. This is preferred.

이때 매개산화반응의 온도는 상온 내지 100℃에서 수행하며, 캐소드액의 운전온도는 상온 내지 70℃가 바람직하다.At this time, the temperature of the mediated oxidation reaction is carried out at room temperature to 100 ℃, the operating temperature of the catholyte is preferably from room temperature to 70 ℃.

아래에 실시예를 통하여 본 발명을 더 구체적으로 설명한다. 단, 하기 실시예는 본 발명의 예시에 불과한 것으로서 본 발명의 특허청구범위가 이에 따라 한정되는 것은 아니다.The present invention will be described in more detail with reference to the following Examples. However, the following examples are merely examples of the present invention, and the claims of the present invention are not limited thereto.

[실시예]EXAMPLE

매개 금속이온으로 Ce과 Ag를 이용하는 전기화학적 매개산화(Mediated Electrochemical Oxidation, MEO)공정을 도 2에 나타낸 바와 같은 장치에서 악취가스의 처리에 대한 실험을 진행하였다.Experiments on the treatment of malodorous gas were carried out in the apparatus as shown in FIG. 2 using a mediated electrochemical oxidation (MEO) process using Ce and Ag as mediator metal ions.

악취가스는 NH3, H2S 및 CH3SH를 사용하였으며, NH3 20%, H2S 0.1% 및 CH3SH 0.1부피%가 N2와 혼합된 혼합가스를 이용하였으며, 공기와 악취가스는 MFC(Mass Flow Controller)를 이용하여 유속을 제어하여 일정 농도로 희석된 악취가스를 기-액접촉매개산화스크러버(10)에 공급하여 실험을 수행하였다.As odor gas, NH 3 , H 2 S and CH 3 SH were used, NH 3 20%, H 2 S 0.1% and CH 3 SH 0.1% by volume were mixed with N 2 , air and odor gas The experiment was performed by controlling the flow rate using MFC (Mass Flow Controller) to supply the odor gas diluted to a certain concentration to the gas-liquid contact medium oxidation scrubber (10).

매개 금속이온으로 사용된 Ce과 Ag는 악취가스 분해실험이 실시되기 전, 격막인 나피온(Nafion) 324에 의해 아노드실과 캐소드실이 분리된 전해셀(전극 면적 약 140㎠, 전극은 DSA mesh type 전극)에 10A의 전류를 공급함으로써 Ce(IV) 및 Ag(II)로 산화시켰고, 악취가스가 처리되는 동안에도 전해셀에 계속 10A의 전류를 공급하여 악취의 분해에 의해 Ce(III)와 Ag(I)으로 환원된 매개 금속이온을 연속적으로 산화시키면서 Ce(IV)와 Ag(II)에 의한 악취가스의 분해 실험을 수행하였다.Ce and Ag used as intermediary metal ions are electrolytic cells in which anode and cathode chambers are separated by Nafion 324 as a diaphragm before conducting odor gas decomposition experiments. type electrode) to oxidize Ce (IV) and Ag (II) by supplying a current of 10A, while supplying a current of 10A to the electrolytic cell while the malodorous gas is being processed. The decomposition of odor gas by Ce (IV) and Ag (II) was carried out while continuously oxidizing the mediated metal ions reduced to Ag (I).

이 때 스크러버(10)의 내경은 φ10cm이고, 높이는 90cm이며, Ag(II) 및 Ce(IV)가 포함된 아노드액에 의해 악취가스가 분해되는 실제구간은 충전재(packing material)가 충진되어 있는 높이 60cm내에서 가스와 아노드액이 접촉하여 분해처리 된다. 스크러버(10) 내에는 Ce(IV)와 Ag(II) 및 질산 전해질에 의해 쉽게 분해되지 않으며 내산성 및 내구성이 강한 테프론(teflon) 계열의 충전재(Tri-Pack, PFA, Jaeger Products iNC.)를 충진하여 악취가스와 Ce(IV) 및 Ag(II)이 포함된 전해질과의 접촉이 보다 잘 이뤄질 수 있도록 하였다.In this case, the inner diameter of the scrubber 10 is φ10 cm, the height is 90 cm, and the actual section in which the odor gas is decomposed by the anolyte containing Ag (II) and Ce (IV) is filled with a packing material. The gas and the anolyte contact and decompose within 60cm in height. The scrubber 10 is filled with Teflon-based fillers (Tri-Pack, PFA, Jaeger Products iNC.) That are not easily decomposed by Ce (IV), Ag (II), and nitric acid electrolytes, and are highly resistant to acid and durability. Therefore, the odor gas was better contacted with the electrolyte containing Ce (IV) and Ag (II).

[실시예 1] NH3의 분해 처리Example 1 Decomposition of NH 3

캐리어 가스인 공기의 유속 3.1L/min에서 NH3의 유속을 조절하여 스크러버(10)에 도입되는 가스(Air+NH3 혼합가스) 내 NH3의 농도가 22.6ppm이 되도록 조절하였다.The flow rate of NH 3 was controlled at a flow rate of 3.1 L / min of air, which is a carrier gas, so that the concentration of NH 3 in the gas (air + NH 3 mixed gas) introduced into the scrubber 10 was adjusted to 22.6 ppm.

Ce과 Ag에 의한 NH3의 분해를 알아보기 위해 10A의 전류가 공급되는 전해셀에 0.45M Ce(IV)과 3M HNO3이 혼합된 용액과 0.024M Ag(II)와 6M HNO3가 혼합된 용액에 NH3가 혼합된 가스를 주입하면서 시간에 따른 NH3의 분해효율을 측정하였다. 이 두 용액의 부피는 200ml이며, 용액의 온도는 25℃로 일정하게 유지하며 실험을 수행하였다. 또한, 비교를 위해 매개이온이 혼합되지 않은 3M HNO3 및 6M HNO3에 대하여도 동일한 조건으로 NH3 분해효율을 측정하였다.To investigate the decomposition of NH 3 by Ce and Ag, a solution containing 0.45 M Ce (IV) and 3M HNO 3 , and 0.024 M Ag (II) and 6M HNO 3 were mixed in an electrolytic cell supplied with 10 A of current. Decomposition efficiency of NH 3 over time was measured while injecting a gas mixed with NH 3 into the solution. The volume of these two solutions was 200 ml, and the experiment was carried out while keeping the temperature of the solution constant at 25 ° C. Also, for comparison, NH 3 decomposition efficiency was measured under the same conditions for 3M HNO 3 and 6M HNO 3 with no intermediary ions mixed.

도 3은 본 실시예에 따른 Ce(IV) 및 Ag(II)에 의한 NH3의 분해효율과 질산(3M HNO3 및 6M HNO3)에 의한 NH3의 흡수효율을 비교한 결과를 나타낸 것으로서, 3M의 질산용액에서와 0.45M Ce(IV)과 3M HNO3이 혼합된 MEO 용액에서 NH3의 처리효율을 비교한 결과, Ce(IV)가 포함된 MEO 용액에서는 질산만으로 NH3를 처리한 경우에 비해 약 10% 이상의 제거효율을 보이며, 6M 질산용액에서와 0.024M Ag(II)와 6M HNO3가 혼합된 용액에서의 처리효율에서도 10%정도의 차이를 나타내었다. 이것은 질산용액에 흡수되지 못한 NH3가 Ce(IV) 및 Ag(II)에 의해 제거됨으로써 질산용액만을 이용한 경우에 비해 높은 처리효율을 나타냄을 알 수 있다.FIG. 3 shows the results of comparing the decomposition efficiency of NH 3 by Ce (IV) and Ag (II) and the absorption efficiency of NH 3 by nitric acid (3M HNO 3 and 6M HNO 3 ) according to the present embodiment. in the nitric acid solution of 3M and 0.45M Ce (IV) and the MEO solution is mixed 3M HNO 3 comparison of the treatment efficiency of the NH 3, the MEO solution containing a Ce (IV) when treated with NH 3 with only nitric acid The removal efficiency was about 10% higher than that in the 6M nitric acid solution and about 10% in the treatment efficiency of 0.024M Ag (II) and 6M HNO 3 . It can be seen that NH 3 , which has not been absorbed by the nitric acid solution, is removed by Ce (IV) and Ag (II), and thus exhibits a higher treatment efficiency than the case where only nitric acid solution is used.

[실시예 2] H2S의 분해 처리Example 2 Decomposition of H 2 S

캐리어 가스인 공기의 유속 10.5L/min에서 H2S의 유속을 조절하여 스크러버에 도입되는 가스(Air+H2S 혼합가스) 내 H2S의 농도가 10.4ppm이 되도록 조절하였다.The flow rate of H 2 S was adjusted at a flow rate of 10.5 L / min of air, which is a carrier gas, so that the concentration of H 2 S in the gas (air + H 2 S mixed gas) introduced into the scrubber was adjusted to 10.4 ppm.

Ce과 Ag에 의한 H2S의 분해를 알아보기 위해 10A의 전류가 공급되는 전해셀에 0.5M Ce(III)과 3M HNO3이 혼합된 용액과 0.1M Ag(I)와 6M HNO3가 혼합된 용액을 각각 공급하여 Ce(III)는 70%, Ag(I)는 3% 정도 산화시켜 매개산화 이온의 농도를 Ce(Ⅳ)는 0.35M, Ag(Ⅱ)는 0.003M이 되도록하고 H2S를 스크러버에 공급하면서 분해 실험을 수행하였다. 이 두 용액의 부피는 200ml이며, 용액의 온도는 25℃로 일정하게 유지하며 실험을 수행하였다.To investigate the decomposition of H 2 S by Ce and Ag, a solution containing 0.5M Ce (III) and 3M HNO 3 , 0.1M Ag (I), and 6M HNO 3 were mixed in an electrolytic cell supplied with 10A of current. Prepared solutions were oxidized to 70% of Ce (III) and 3% of Ag (I) so that the concentration of mediated ions was 0.35M for Ce (IV) and 0.003M for Ag (II), and H 2 Decomposition experiments were performed while feeding S to the scrubber. The volume of these two solutions was 200 ml, and the experiment was carried out while keeping the temperature of the solution constant at 25 ° C.

도 4는 25℃에서 Ce(IV)와 Ag(II)에 의한 H2S의 분해율을 반응 시간에 따라 나타낸 것이다. Ce(IV)와 Ag(II)에 의해 H2S는 95% 이상 분해처리 됨을 알 수 있었고, Ag(II)를 이용한 경우 H2S가 분해율 100%로 처리되어 Ce(IV)에서 보다 더 높은 분해율을 나타내었다. 이것은 Ag(II)의 산화·환원 전위가 Ce(IV)보다 약 0.2V 정도 높은 것에서 기인한 것으로 보이며, 저온에서의 산화·분해 능력이 Ce(IV)에 비해 우수하다는 것을 보여준다.Figure 4 shows the decomposition rate of H 2 S by Ce (IV) and Ag (II) at 25 ℃ according to the reaction time. It was found that H 2 S was decomposed more than 95% by Ce (IV) and Ag (II). When Ag (II) was used, H 2 S was decomposed at 100% and higher than that of Ce (IV). Degradation rate is shown. This may be due to the oxidation / reduction potential of Ag (II) being about 0.2V higher than that of Ce (IV), which shows that the oxidation / reduction ability at low temperature is superior to Ce (IV).

[실시예 3] 가스 유속에 따른 H2S의 분해 처리Example 3 Decomposition of H 2 S According to Gas Flow Rate

캐리어 가스인 공기의 유속을 10.5, 25, 35L/min으로 증가하면서 Ag(II)에 의한 10.5ppm H2S의 분해 처리를 진행하는 것을 제외하고는 실시예 2와 동일하게 진행하였다.It proceeded in the same manner as in Example 2 except that the decomposition process of 10.5 ppm H 2 S by Ag (II) was carried out while increasing the flow rate of air, which is a carrier gas, to 10.5, 25, 35 L / min.

도 5는 스크러버에 도입되는 가스의 유속에 따라 Ag(II)에 의한 10.5ppm H2S의 분해 경향을 나타낸 것이다. 도 5에 나타난 바와 같이 모든 가스 유속에서 H2S는 Ag(II)에 의해 100% 제거됨을 알 수 있었다.Figure 5 shows the tendency of decomposition of 10.5ppm H 2 S by Ag (II) according to the flow rate of the gas introduced into the scrubber. As shown in FIG. 5, H 2 S was removed 100% by Ag (II) at all gas flow rates.

[실시예 4] CH3SH의 분해 처리Example 4 Decomposition of CH 3 SH

캐리어 가스인 공기의 유속을 11L/min에서 CH3SH의 유속을 조절하여 스크러버에 도입되는 가스(Air+CH3SH 혼합가스) 내 CH3SH의 농도가 10ppm이 되도록 조절하였다.The carrier gas was adjusted to a flow rate of air to adjust the flow rate of CH 3 SH at 11L / min and the concentration of CH 3 SH gas (Air + CH 3 SH gas mixture) is introduced into the scrubber to be 10ppm.

3M HNO3 용액만이 상부 노즐을 통해 공급되는 스크러버에 CH3SH를 주입하여 질산에 의한 CH3SH의 분해율과 10A의 전류가 공급되는 전해셀에 0.1M Ag(I)과 3M HNO3이 혼합된 용액을 공급하여 Ag(I)을 3% 정도 산화시킨 후 CH3SH를 스크러버에 공급하면서 질산과 Ag(II)에 의한 CH3SH의 분해를 비교하였다. 상기 용액의 부피는 2000ml이며, 용액의 온도는 25℃로 일정하게 유지하며 실험을 수행하였으며, 그 결과를 도 6 및 도 7에 도시하였다.Only 3M HNO 3 solution injects CH 3 SH into the scrubber supplied through the upper nozzle, so that 0.1M Ag (I) and 3M HNO 3 are mixed in the electrolysis cell supplied with 10A current and decomposition rate of CH 3 SH by nitric acid. Ag (I) was oxidized about 3% by supplying the prepared solution, and CH 3 SH was supplied to the scrubber, and the decomposition of CH 3 SH by nitric acid and Ag (II) was compared. The volume of the solution is 2000ml, the experiment was carried out while keeping the temperature of the solution constant at 25 ℃, the results are shown in Figures 6 and 7.

도 6에서 보이는 바와 같이 질산에 의한 CH3SH의 분해는 반응이 진행되면서 용액 내 질산의 함량이 줄어들어 CH3SH의 분해율 또한 감소함을 보이고 있으나, Ag(II)이 존재하는 경우, Ag(II)에 의해 지속적으로 CH3SH가 분해됨을 알 수 있다. 이것은 CH3SH의 분해로 환원된 Ag(I)는 전해셀에서 산화되어 다시 Ag(II)로 산화되고, 이 재산화된 Ag(II)에 의해 CH3SH 분해가 지속적으로 진행됨으로써 CH3SH를 완전히 처리할 수 있음을 나타내고 있다.As shown in FIG. 6, the decomposition of CH 3 SH by nitric acid shows that the content of nitric acid in the solution decreases as the reaction proceeds, but the decomposition rate of CH 3 SH also decreases, but when Ag (II) is present, Ag (II) It can be seen that CH 3 SH is continuously degraded by). This is delivered is a Ag (I) reduction in decomposition of CH 3 SH oxidation in cells and oxidized back to the Ag (II), being a re-oxidation of the CH 3 SH decomposed by Ag (II) proceeds continuously CH 3 SH Indicates that it can be processed completely.

도 7은 반응 시간에 따라 Ag(II)에 의한 CH3SH 분해율 및 이로인해 발생되는 CO2를 발생량을 나타낸 것으로, 도 7의 결과를 참조하면 CH3SH는 Ag(II)에 의해 분해되고, CH3SH의 분해로 환원된 Ag는 전해셀에서 다시 산화되는 과정에 의해 CH3SH를 지속적으로 처리함으로써 CH3SH가 완전히 제거되며, CH3SH의 지속적인 분해로 CO2 또한 계속 발생되고 있음을 보여준다. Figure 7 shows the CH 3 SH decomposition rate and the amount of CO 2 generated by Ag (II) according to the reaction time, referring to the results of Figure 7 CH 3 SH is decomposed by Ag (II), reduced to CH 3 SH decomposition of Ag is delivered that by treating the CH 3 SH by the process of oxidation again in continuous cell CH 3 SH is is completely removed, CO 2 also continues to generate the continuous decomposition of CH 3 SH Shows.

본 발명의 실시예의 결과로부터 NH3, H2S 및 CH3SH는 Ag(II)에 의해 90%이상 분해됨을 알 수 있었고, 특히 H2S와 CH3SH는 Ag(II)에 의해 상온에서 완벽히 제거될 수 있음을 확인하였다.From the results of the examples of the present invention, it can be seen that NH 3 , H 2 S and CH 3 SH are decomposed more than 90% by Ag (II), in particular H 2 S and CH 3 SH by Ag (II) at room temperature It was confirmed that it could be completely removed.

또한 스크러버로부터 배출되는 가스 중 포함된 수분, 매개 금속이온 및 질산은 열교환기를 통해 95% 이상을 회수하였으며, 이 결과로부터 Ag을 이용하는 MEO 공정에 의해 NH3, H2S 및 CH3SH로 대표되는 악취가스를 지속적으로 처리할 수 있음을 알 수 있다.In addition, more than 95% of the water, the mediated metal ions, and nitric acid contained in the gas discharged from the scrubber were recovered through a heat exchanger. From this result, the odor represented by NH 3 , H 2 S and CH 3 SH by the MEO process using Ag was obtained. It can be seen that the gas can be treated continuously.

본 발명에 따른 장치는 전기화학적 매개산화방법을 이용한 돈사 및 계사에서 발생되는 H2S, CH3SH, NH3 등을 포함한 악취가스 제거장치로서 악취가스 혼합물을 Ce(Ⅳ) 또는 Ag(Ⅱ) 등의 매개이온이 함유된 용액에 기-액접촉시켜 악취가스를 효율적으로 처리할 수 있어 매개산화반응조의 크기가 작아지는 장점이 있으며, 또한 일체형 스크러버식 산화반응조를 적용함으로서 장치가 단순화되어 초기 장치 투자비와 운전의 용이성이 있다. The apparatus according to the present invention is a odor gas removal device including H 2 S, CH 3 SH, NH 3 and the like generated in pigs and cages using an electrochemical mediated oxidation method, Ce (IV) or Ag (II) The gas-liquid contact with the solution containing the mediated ions can effectively treat the odor gas, thereby reducing the size of the mediated oxidation tank, and simplifying the device by applying the integrated scrubber-type oxidation tank. There are investment costs and ease of operation.

Claims (7)

유입된 악취가스혼합물이 매개이온에 의하여 매개산화되는 충진재로 충진된 기-액접촉매개산화스크러버;A gas-liquid contact mediated scrubber filled with a filler in which the odor gas mixture introduced is mediated by mediated ions; 상기 기-액접촉매개산화스크러버의 상부에 연결되고 전해셀의 아노드실에서 생성되는 매개이온을 분사하는 매개이온도입관;A medium temperature inlet pipe connected to an upper portion of the gas-liquid contact mediated oxidation scrubber and spraying a medium ion generated in an anode chamber of an electrolysis cell; 상기 기-액접촉매개산화스크러버의 하단부에서 악취가스혼합물을 도입하는 악취가스도입관;Odor gas introduction pipe for introducing an odor gas mixture at the lower end of the gas-liquid contact mediated oxidation scrubber; 상기 기-액접촉매개산화스크러버로부터 악취가스 접촉에 의해 환원된 매개이온을 회수하는 회수관을 통하여 아노드액을 저장하고 아노드액을 전해셀의 아노드실로 주입하는 아노드액저장조;An anode liquid storage tank for storing an anolyte solution and injecting the anolyte solution into an anode chamber of an electrolytic cell from a gas-liquid contact mediated oxidation scrubber through a recovery tube for recovering mediated ions reduced by malodor gas contact; 상기 아노드액저장조와 물질균형을 맞추기 위한 캐소드액저장조; 및A catholyte storage tank for matching material balance with the anolyte storage tank; And 상기 기-액접촉매개산화스크러버의 상부에 구비된 분해가스배출관에 연결되어 기-액접촉매개산화스크러버로부터 배출되는 수분, 매개 금속이온 또는 질산을 포집하여 상기 아노드액 저장조로 회수하는 전기집진장치 또는 열교환기; Electrostatic precipitator which is connected to the decomposition gas discharge pipe provided in the upper portion of the gas-liquid contact medium oxidation scrubber to collect the water, medial metal ions or nitric acid discharged from the gas-liquid contact medium oxidation scrubber to recover the anode liquid storage tank Or heat exchanger; 를 구비하는 전기화학적 매개산화 악취가스 처리장치.Electrochemical mediated odor gas treatment device having a. 제 1항에 있어서,The method of claim 1, 상기 악취가스는 암모니아, H2S, CH3SH 또는 이의 혼합물인 것을 특징으로 하는 전기화학적 매개산화 악취가스 처리장치.The malodor gas is an ammonia, H 2 S, CH 3 SH or an electrochemical mediated odor gas treatment device, characterized in that a mixture thereof. 삭제delete 제 1항에 있어서,The method of claim 1, 상기 전해셀은 아노드실, 케소드실 및 전해격막으로 구성되고, 정류기에 의해 전류가 공급되어 매개이온을 산화하는 것을 특징으로 하는 전기화학적 매개산화 악취가스 처리장치.The electrolytic cell is composed of an anode chamber, a cathode chamber and an electrolytic diaphragm, electrochemical mediated odor gas treatment apparatus characterized in that the current is supplied by the rectifier to oxidize the mediated ions. 삭제delete 삭제delete 제 1항에 있어서,The method of claim 1, 상기 매개 이온은 세륨이온(Ce3+) 또는 은이온(Ag+)이고, 양극액과 음극액은 질산 수용액 또는 황산 수용액인 것을 특징으로 하는 전기화학적 매개산화 악취가스 처리장치. The mediating ion is cerium ion (Ce 3+ ) or silver ion (Ag + ), and the anolyte and the catholyte are an electrochemically mediated odor gas treatment device, characterized in that the aqueous solution of nitric acid or sulfuric acid.
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KR101338287B1 (en) 2011-11-29 2013-12-09 순천대학교 산학협력단 Oxidation Method of Electro-activated Catalyst to Apply in Odor Gases Removal, And Oxidation Apparatus Thereof
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