KR20000065466A - Method for treating waste gas and manufacturing by-product chemicals simultaneously - Google Patents

Method for treating waste gas and manufacturing by-product chemicals simultaneously Download PDF

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KR20000065466A
KR20000065466A KR1019990011777A KR19990011777A KR20000065466A KR 20000065466 A KR20000065466 A KR 20000065466A KR 1019990011777 A KR1019990011777 A KR 1019990011777A KR 19990011777 A KR19990011777 A KR 19990011777A KR 20000065466 A KR20000065466 A KR 20000065466A
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exhaust gas
gas
solution
absorption tower
neutralization
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KR1019990011777A
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Korean (ko)
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이희철
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이희철
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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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/60—Simultaneously removing sulfur oxides and nitrogen oxides
    • 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
    • B01D53/14—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 absorption
    • B01D53/1456—Removing acid components
    • B01D53/1481—Removing sulfur dioxide or sulfur trioxide
    • 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
    • B01D53/14—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 absorption
    • B01D53/1493—Selection of liquid materials for use as absorbents
    • 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
    • B01D53/86—Catalytic processes
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B01D53/8631—Processes characterised by a specific device
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/30—Alkali metal compounds
    • B01D2251/304—Alkali metal compounds of sodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/60—Inorganic bases or salts
    • B01D2251/604—Hydroxides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Environmental & Geological Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Treating Waste Gases (AREA)

Abstract

PURPOSE: Are provided a waste gas disposal and the method for the preparation of disposal by-product, which divides toxic substance such as SOx or NOx contained in waste gas as each ingredient by using neutralization and oxidation reaction and can use the by-product as chemicals. CONSTITUTION: The waste gas disposal and the method for preparation of disposal by-product comprises; the first process of collecting the whole quantity of SOx and the portion quantity of NOx as neutralization by surface contact to apply waste gas to the first absorption column(10) sprayed sodium hydroxide solution, and obtaining liqueified SO2 through compressing and cooling after dividing the solution, if SOx is changed into acidic sodium sulfite, heating and drying to discharge as sulfur dioxide; the second process of making nitrogen dioxide by oxidation reaction the gas mixture removed SO2 at the catalytic reactor(40) and obtaining nitric acid by dissolving in water at the second column(70); and the third process of recovery of and crystallizing Na2CO3 solution by neutralization reaction at the third absorption column(80) spraying the other mixture exhausted from the second absorption column(70) on the sodium hydroxide solution and discharging remained gas to atmosphere.

Description

배기가스 처리와 처리 부산물의 제조방법{Method for treating waste gas and manufacturing by-product chemicals simultaneously}Method for treating waste gas and manufacturing by-product chemicals simultaneously

본 발명은 배기가스 처리와 처리부산물의 제조방법에 관한 것으로, 더욱 상세하게는 배기가스에 함유된 SOx나 NOx 등의 유해물질을 중화반응과 산화반응을 이용하여 성분별로 분리하고, 그 부산물을 화공약품으로 사용할 수 있도록 하는 배기가스 처리와 처리 부산물의 제조방법에 관한 것이다.The present invention relates to an exhaust gas treatment and a method for producing by-products, and more particularly, to separate harmful substances such as SOx and NOx contained in the exhaust gas by components using neutralization and oxidation reactions, and by-products thereof. The present invention relates to an exhaust gas treatment and a manufacturing method of a by-product for use as a chemical.

오늘날 산업기술의 발달과 함께 생활환경을 침해하는 요인으로 사회적인 문제로 대두되고 있는 공해는 크게 대기오염, 수질오염, 그리고 소음공해 등으로 구분할 수 있다.Pollution, which is emerging as a social problem as a factor invading the living environment with the development of industrial technology, can be classified into air pollution, water pollution, and noise pollution.

특히, 대기오염은 여러 가지 발생원인이 있으나 자동차나 대형건물의 난방용으로 사용되는 화석 연료인 유류나 공장이나 발전소 등에서 연료로 사용되는 석탄이나 석유를 연소시켜서 생성되는 배기가스가 주된 원인이 되는 물질이다.In particular, air pollution has various causes, but the main source is the exhaust gas generated by burning coal or petroleum, which is used as fuel in oils, factories, and power plants, which are used for heating cars and large buildings. .

보통, 석탄이나 중유 등을 연소시켜 생성된 배기가스에는 대기로 배출되어도 해가 되지 않는 수증기와 유해물질로서 SOx, NOx, CO2, CO 등과 약간의 납 산화물을 함유하고 있다.Usually, in the exhaust gas generated by combustion of coal or heavy oil, etc., it contains some dross as SOx, NOx, CO 2, CO and water vapor as a harmful substance that is not harmful even if released into the atmosphere.

이러한 배기가스로부터 유해한 물질을 중화시켜 대기오염을 줄이기 위한 방법으로 석회석을 이용하여 유해물질을 흡수 처리하는 석고법(건식 또는 습식으로 유해물질을 흡수처리하는 공법)을 사용하였다.As a method of neutralizing harmful substances from such exhaust gases and reducing air pollution, a gypsum method (dry or wet absorption method) is used to absorb harmful substances using limestone.

그렇지만, 기존의 석고법은 유해물질을 제거하기 위한 설비장비 자체가 커서 이에 따른 설치면적과 비용이 과다하게 드는 문제가 있고, 특히 유해물질을 제거하여 생성된 석고가 제 2의 공해물질로 남아 이에 대한 개선이 필요하게 되었다.However, the existing gypsum method has a problem of excessive installation area and cost due to the large equipment for removing harmful substances, and in particular, gypsum produced by removing harmful substances remains as a second pollutant. Improvements were needed.

따라서, 본 발명에서는 상기와 같은 제 2공해물질이 생기지 않고 배기가스에서 SOx, NOX, CO2등의 유해물질을 포집· 분리하되, 각 공정에서 얻어지는 부산물을 재활용할 수 있도록 하여 간단한 공정으로 배기가스 처리효율을 높히면서 경제적인 효과도 기대할 수 있도록 개선한 배기가스 처리와 처리 부산물의 제조방법을 제공하는데 그 목적이 있다.Therefore, in the present invention, the second pollutant does not occur as described above, but collects and separates harmful substances such as SOx, NO X , and CO 2 from the exhaust gas, and by-products obtained in each process can be recycled to exhaust the gas in a simple process. The purpose of the present invention is to provide an improved method for treating exhaust gas and producing by-products to improve the gas treatment efficiency and to expect economic effects.

도 1은 본 발명에 따른 배기가스 처리장치를 나타내는 개략도.1 is a schematic view showing an exhaust gas treating apparatus according to the present invention.

＜도면의 주요 부분에 대한 부호의 설명＞<Description of the code | symbol about the principal part of drawing>

1 : NaOH(aq) 탱크2 : Na2SO3(aq) 탱크1: NaOH (aq) tank 2: Na 2 SO 3 (aq) tank

10 : 제 1흡수탑(충진형)20 : 증발관10: first absorption tower (fill type) 20: evaporation tube

30 : 건조기40 : 촉매반응기30: dryer 40: catalytic reactor

50 : 압축기(저압용)60 : 냉각조50: compressor (low pressure) 60: cooling tank

70 : 제 2흡수탑80 : 제 3흡수탑70: second absorption tower 80: third absorption tower

90 : 증발관100 : 결정조90: evaporation tube 100: crystal bath

본 발명은 가성소다 용액이 분사되는 제 1흡수탑(10)에 배기가스를 공급하여 표면접촉에 의한 중화반응으로 SOX전량과 NOX일부를 포집하고, SOx가 전부 산성아황산소다 수용액(NaHSO3)이 되면 이 수용액을 분리하여 가열한 다음 아황산 가스로 배출시켜서 건조기를 통과시킨 다음 압축과 냉각하는 과정을 거쳐 액화 SO2를 얻는 제 1공정과; SO2가 제거된 기체 혼합물을 촉매반응기(40)에서 산화반응시켜서 이산화질소를 만들고 제 2흡수탑(70)에서 물에 용해시켜 질산(HNO3)을 얻는 제 2공정과; 그리고, 제 2흡수탑(70)에서 배기되는 나머지 혼합물을 가성소다 용액을 분사하는 제 3흡수탑(80)에서 중화반응시켜 Na2CO3용액을 회수하고 남은 가스를 대기로 배출하는 제 3공정으로 이루어진 것이다.The invention caustic soda solution is sprayed the first absorption tower (10) neutralization by the surface in contact with the exhaust gas fed to the SO X amount and the NO X trapping part, and SOx are all acidic sulfite soda aqueous solution to which (NaHSO 3 A) first step of obtaining liquefied SO 2 by separating and heating the aqueous solution, then discharging it into sulfurous acid gas, passing it through a dryer, and then compressing and cooling; A second step of oxidizing the gas mixture from which SO 2 is removed in the catalytic reactor 40 to produce nitrogen dioxide and dissolving it in water in the second absorption tower 70 to obtain nitric acid (HNO 3 ); In addition, a third process of neutralizing the remaining mixture exhausted from the second absorption tower 70 in the third absorption tower 80 injecting the caustic soda solution to recover the Na 2 CO 3 solution and discharge the remaining gas to the atmosphere It is made up of.

이하, 본 발명에 따른 배기가스 처리장치를 개략적으로 나타내는 첨부도면 1을 참조하여 본 발명을 보다 상세하게 설명하면 다음과 같다.Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings 1 schematically showing an exhaust gas treating apparatus according to the present invention.

본 발명은 석탄이나 중유 등의 화석연료를 사용하여 생성된 배기가스에 포함되어 있는 유해물질을 성분별로 제거하여 생성된 부산물을 화학약품으로 다시 사용할 수 있게 하는 배기가스 처리와 처리 부산물의 제조방법에 관한 것으로, 배기가스를 3개의 흡수탑(10,70,80)에 차례대로 공급되어 배기가스에 함유된 각 유해물질이 중화반응과 산화반응 등에 의하여 차례로 흡수 제거하고 남은 과잉 공기만이 대기로 배출되고, 그 과정에서 얻어지는 부산물을 화공약품으로 사용할 수 있도록 농축 처리함으로써, 간단한 장치를 이용하여 유해물의 처리효율을 높일 수 있고, 또한 그 부산물을 다시 사용할 수 있게 한 것이다.The present invention relates to a method for producing exhaust gas treatment and treatment by-products by removing harmful substances contained in exhaust gases generated by using fossil fuels such as coal or heavy oil, by component, and allowing the generated by-products to be used again as chemicals. In this regard, exhaust gas is supplied to three absorption towers 10, 70, and 80 sequentially, and each harmful substance contained in the exhaust gas is sequentially absorbed and removed by neutralization reaction and oxidation reaction, and only the remaining excess air is discharged to the atmosphere. By concentrating the by-products obtained in the process to be used as chemicals, it is possible to increase the treatment efficiency of the harmful substances using a simple device, and also to use the by-products again.

여기서, 본 발명에 따라 배기가스를 처리하기 위한 장치는 가성소다수용액을 분사하여 배기가스와 표면접촉으로 중화반응을 유도하는 제 1흡수탑(10)과, SOx의 계속된 흡수로 생성된 NaHSO3용액을 Na2SO3용액과 SO2가스로 분리시켜주는 증발관(20)과, 상기 SO2가스에서 습기를 제거하고 압축하여 액화시켜주는 건조기(30) 및 압축기(50) 및 냉각조(60)와, 이 SO2가 분리되고 남은 기체 혼합물을 공급받아 그 중에 함유된 NOx를 전부 NO2가스로 변화시켜 주는 촉매반응기(40) 및 NO2가스를 물과 반응시켜 질산(HNO3)으로 회수하는 제 2흡수탑(70)과, 나머지 기체 혼합물을 공급받아 가성소다 수용액으로 흡수·순환시켜 Na2CO3을 얻는 제 3흡수탑(80)과, 이 Na2CO3을 농축하여 증발관(90)에서 과포화 상태로 만든 다음 Na2CO3결정으로 추출하는 결정조(100)로 구성되어 있다.Here, the apparatus for treating exhaust gas according to the present invention comprises a first absorption tower 10 for injecting caustic soda solution to induce a neutralization reaction in surface contact with the exhaust gas, and NaHSO 3 generated by continuous absorption of SOx. An evaporation tube 20 which separates the solution into a Na 2 SO 3 solution and a SO 2 gas, and a dryer 30, a compressor 50, and a cooling tank 60 to remove moisture from the SO 2 gas and to liquefy it. ) and, as the SO 2 is separated catalytic reactor (40) and nitric acid (HNO 3) is reacted with the NO 2 gas with water, which is changed to the NOx all to NO 2 gas contained in that when supplied with the rest of the gas mixture recovered a second absorber (70) and, when supplied with the remaining gas mixture by absorption and circulation with caustic soda aqueous Na 2 CO 3 the third absorption tower 80, to get and, by concentration of the Na 2 CO 3 evaporation tube ( 90) consists of the following crystal-100 to extract the Na 2 CO 3 crystals made in a supersaturated state in the It can control.

이를 좀더 상세하게 설명하면, 본 발명에 따른 배기가스 처리방법은 배기가스에 함유된 SOx와 NOx 그리고 CO2를 단계적으로 분리하게 되는 것이다.In more detail, the exhaust gas treatment method according to the present invention is to phase-separate SOx, NOx and CO 2 contained in the exhaust gas.

제 1공정에서는 배기가스를 가성소다수용액인 NaOH(aq)가 분사되고 제 1흡수탑(10)를 통과시켜 SOx를 중화반응을 일으키게 된다.In the first process, NaOH (aq), which is a caustic soda solution, is injected into the exhaust gas, and the SOx is neutralized by passing through the first absorption tower 10.

이때, 고온의 가스상태로 배기가스에 포함된 SOx는 액체 상태인 가성소다수용액과 표면접촉에 의해 아황산소다용액(Na2SO3)으로 다음 반응식 (1)과 같이 중화가 되면서 물이 생성되며, 이 아황산소다용액은 다시 SO2를 흡수하여 반응식 (2)와 같이 2NaHSO3을 얻게 된다.At this time, SOx contained in the exhaust gas in a hot gas state is neutralized with sodium sulfite solution (Na 2 SO 3 ) by surface contact with a caustic soda solution in a liquid state as shown in the following Reaction Formula (1), This sodium sulfite solution absorbs SO 2 again to obtain 2NaHSO 3 as in Scheme (2).

2NaOH + SO2→ Na2SO3+ H2O2NaOH + SO 2 → Na 2 SO 3 + H 2 O

Na2SO3+ SO2+ H2O → 2NaHSO3 Na 2 SO 3 + SO 2 + H 2 O → 2 NaHSO 3

특히, 상기 반응식 (2)에서 가스의 온도가 100℃ 이상이 되면 역반응이 일어나 SO2가 생성이 되는데, 이때의 가스 온도는 용액과 가스의 표면접촉에 의해 증발열이 액체인 가성소다 수용액으로 열전달이 이루어짐에 따라 50℃ 이하를 유지시켜 역반응을 억제시키게 된다.In particular, in the reaction formula (2), when the temperature of the gas is 100 ° C. or more, a reverse reaction occurs and SO 2 is generated. At this time, the heat is transferred to the aqueous solution of caustic soda in which the evaporative heat is liquid by the surface contact of the solution and the gas. As a result it is kept below 50 ℃ to suppress the reverse reaction.

본 발명의 바람직한 구현예에 따르면, 상기 흡수탑(10)에는 첨부도면에서 도시되지는 않았지만 별도로 냉각기를 설치하여, 반응식 (2)에서 흡수탑(10)의 내부 온도가 100℃ 이상으로 높아져서 역반응이 일어나지 않도록 증발열의 열전달과 함께 냉각효율을 높일 수 있게 하는 것이 바람직하다.According to a preferred embodiment of the present invention, the absorption tower 10 is not shown in the accompanying drawings, but provided with a separate cooler, in the reaction formula (2) the internal temperature of the absorption tower 10 is raised to more than 100 ℃ reverse reaction is It is desirable to be able to increase the cooling efficiency with the heat transfer of the evaporation heat so as not to occur.

이렇게 상기 흡수탑(10)으로부터 분리된 산성 아황산소다 수용액은 증발관(20)으로 보내지게 되며, 여기서 아황산소다 수용액을 100℃ 온도로 가열하여 Na2SO3용액과 SO2를 분리하고, 이렇게 분리된 Na2HSO3농축액은 상기 흡수탑(10)으로 재순환되기 위하여 2개의 탱크(1,2)중에서 어느 하나에 저장되었다가 SO2흡수에 다시 사용된다.The acidic sodium sulfite solution separated from the absorption tower 10 is sent to the evaporation tube 20, where the sodium sulfite solution is heated to 100 ° C. to separate Na 2 SO 3 solution and SO 2 , and thus The Na 2 HSO 3 concentrate was stored in either of the two tanks (1, 2) for recycling to the absorption tower (10) and used again for SO 2 absorption.

처음 HNO3용액으로 SOx를 흡수하고 그 다음 생성된 Na2SO3수용액이 SOx흡수재로 순환사용된다.The first HNO 3 solution absorbs SOx and the resulting Na 2 SO 3 aqueous solution is circulated to the SOx absorber.

이때, 상기 기체 상태로 남아 있는 SO2는 건조기(30)를 거쳐 압축기(50)로 보내져서 2기압 정도로 압축되고 냉각조(60)에서 냉각되어 액화된다.At this time, the SO 2 remaining in the gaseous state is sent to the compressor 50 through the dryer 30, compressed to about 2 atm, and cooled in the cooling tank 60 to be liquefied.

상기 제 1흡수탑(10)에서 나오는 배기가스에는 NOx와 CO2가스가 함유되어 있고, 이 가스는 NOx의 대부분이 NO로 이루어져 있어서 NO2로 산화시키기 위하여 촉매반응기(40)로 보내지게 되며, 이 NO2로 산화된 혼합기체는 제 2흡수탑(70)에서 물을 흡수하여 질산이 된다.The exhaust gas from the first absorption tower 10 contains NOx and CO 2 gas, which is sent to the catalytic reactor 40 to oxidize to NO 2 because most of the NOx is made of NO, The mixed gas oxidized with NO 2 absorbs water from the second absorption tower 70 to form nitric acid.

이와 같은 반응은 다음과 같이 이루어지게 된다.This reaction is made as follows.

NO + 1/2O2→ NO2 NO + 1 / 2O 2 → NO 2

NO2+ H2O → HNO3 NO 2 + H 2 O → HNO 3

이렇게 생성된 질산은 처음에 묽은 상태이므로 제 2흡수탑(70)에서 순환흡수시켜 적당한 농도에서 배출하여 상품화하게 된다.The nitric acid produced in this way is initially in a dilute state and is circulated and absorbed in the second absorption tower 70 to be discharged at an appropriate concentration to commercialize.

제 3공정은 상기 제 2흡수탑(70)에서 질산으로 분리되고 남은 가스 즉, CO2가 다량 함유된 가스는 제 2흡수탑(80)으로 공급되어 NaOH 용액과 반응하게 되고, 그 결과 Na2CO3화가 이루어진 다음 회수결정화되어 화공약품으로 다시 사용할 수 있게 만들게 되는데, 이러한 반응은 다음과 같은 반응식 (5)으로 나타낼 수 있다.In the third process, the remaining gas separated from nitric acid in the second absorption tower 70, that is, a gas containing a large amount of CO 2 is supplied to the second absorption tower 80 to react with the NaOH solution, and as a result, Na 2 CO 3 is then recovered and crystallized to make it usable as a chemical. This reaction can be represented by the following equation (5).

2NaOH + CO2→ Na2CO3+ H2O2NaOH + CO 2 → Na 2 CO 3 + H 2 O

이와 같이, 본 발명에 따르면 제 1공정에서 SOx를 제거하여 액화 SO2를 생성하고, 제 2공정에서는 NOx를 분리하여 액화 질산을 생성하게 되며, 제 3공정에서는 CO2를 제거하여 Na2CO3가 생성되는 일련의 처리과정이 진행되면 SOx, NOx 등의 유해가스는 제거되고 질산, Na2CO3, 액화 SO2등의 부산물이 회수되어 유해가스의 처리와 함께 부산물을 재활용하는 목적을 동시에 달성할 수 있게 되는 것이다.As described above, according to the present invention, SOx is removed in the first step to generate liquefied SO 2 , and in the second step, NOx is separated to generate liquefied nitric acid, and in the third step, CO 2 is removed to remove Na 2 CO 3. When a series of treatment processes are performed, harmful gases such as SOx and NOx are removed, and by-products such as nitric acid, Na 2 CO 3 and liquefied SO 2 are recovered to achieve the purpose of recycling by-products along with the treatment of harmful gases. You can do it.

이하, 본 발명에 따른 처리방법을 이용하여 실시한 실시예를 살펴보면 다음과 같다.Hereinafter, an embodiment performed using the treatment method according to the present invention will be described.

실시예Example

파편 유리관으로 충진된 3개의 흡수탑과 산화조를 포함하는 본 발명에 따른 처리장치의 비교예에 기술한 것과 거의 같은 가스 조성의 보일러 가스를 공급하고, 이 배기가스를 본 발명에 따른 처리방법으로 처리하였으며, 그 결과는 탈황율은 99%이고, 탈질효율 또한 99% 이상, 그리고 CO2제거율도 99% 이상을 보였다.A boiler gas having a gas composition substantially the same as that described in the comparative example of the treatment apparatus according to the present invention comprising three absorption towers filled with shard glass tubes and an oxidizing tank, and the exhaust gas is treated as a treatment method according to the present invention. The desulfurization rate was 99%, the denitrification efficiency was more than 99%, and the CO 2 removal rate was more than 99%.

비교예Comparative example

실험용인 충진흡수탑에 상부로부터 13% NaOH용액을 분사하면서 밑으로 보일러의 배기가스를 주입하여 실험을 하였으며, 이때의 배기가스에 함유된 유해물질의 조성비는 CO2가 12%, SO2가 530ppm, NOx가 205ppm, 수증기가 13%, O2가 7.1%, 온도는 160℃였다.And while spraying a 13% NaOH solution from the top to the laboratory of filling the absorber injected into the exhaust gas of the boiler below were experiments, the composition ratio of the harmful substances contained in the exhaust gas at this time CO 2 is 12%, SO 2 is 530ppm , NOx was 205 ppm, steam was 13%, O 2 was 7.1%, and temperature was 160 ° C.

상기 흡수탑에서 중화반응을 시킨 결과, SO2가스는 0% 완전히 흡수되었고, NOx는 148ppm으로 28%의 탈질율을 보였으며, CO2의 제거율은 1.8%를 보였다.As a result of neutralization in the absorption tower, SO 2 gas was completely absorbed by 0%, NO x was 148 ppm, showed 28% denitrification rate, and CO 2 removal rate was 1.8%.

이러한 결과는 다음과 같이 흡수탑내에서 반응이 일어나기 때문이다.This is because the reaction takes place in the absorption column as follows.

즉,SO2는 반응식(1)에 의하여 Na2SO3가 되고 CO2는 반응식 (5)에 의하여 Na2CO3가 되나, Na2CO3는 SOx와 다시 반응하여 Na2SO3가 되며 CO2는 유리된다. 이 반응은 다음의 반응식(6)으로 나타낼 수 있다.That is, SO 2 becomes Na 2 SO 3 by Reaction (1) and CO 2 becomes Na 2 CO 3 by Reaction (5), but Na 2 CO 3 reacts with SOx again to become Na 2 SO 3 , and CO 2 is liberated. This reaction can be represented by the following reaction formula (6).

Na2CO3+ SO2→ Na2SO3+ CO2 Na 2 CO 3 + SO 2 → Na 2 SO 3 + CO 2

그러므로, SO2는 전부 반응하는 한편 CO2는 아주 적은 1.8% 정도가 흡수되는 것을 실험에서 알 수 있었다.Therefore, it can be seen from the experiment that all of SO 2 reacts while only about 1.8% of CO 2 is absorbed.

따라서, 화석 연료의 연소로 생성되는 배기가스에서 SO2, CO2와 NOx를 전부 제거하기 위해서는 상술한 바와 같이 3단계 공정을 거쳐 제거할 수 있게 되는 것이다.Therefore, in order to remove all SO 2 , CO 2 and NO x from the exhaust gas generated by the combustion of the fossil fuel, it can be removed through a three step process as described above.

이상에서 본 바와 같이, 본 발명은 배기가스에 포함된 각 유해물질을 반응에 의해 재활용 가능한 화공약품으로 만들어 냄으로 폐자원을 회수하게 되며, 결과적으로 이를 위한 시설비를 회수해 낼 수 있고, 국가적으로 큰 이익을 창출할 수 있게 된다. 특히, 지구 온난화를 일으키는 CO2배출을 줄여야 하는 과제를 동시에 해결하게 된다.As described above, the present invention is to recover the waste resources by making each hazardous substance contained in the exhaust gas into a chemical that can be recycled by the reaction, and as a result can recover the facility cost for this, nationally It can make a big profit. In particular, the task of reducing the CO 2 emissions that cause global warming will be solved simultaneously.

Claims (3)

배기가스로부터 SOx 및 NOx를 포함하는 유해물질을 제거하는 배기가스 처리방법에 있어서,In the exhaust gas treatment method for removing the harmful substances including SOx and NOx from the exhaust gas, 가성소다 용액이 분사되는 제 1흡수탑(10)에 배기가스를 공급하여 표면접촉에 의한 중화반응으로 SOX전량과 NOX일부를 포집하고, SOX가 전부 산성아황산소다 수용액(NaHSO3)이 되면 이 수용액을 분리하여 가열한 다음 아황산 가스로 배출시켜서 건조한 다음 압축과 냉각하는 과정을 거쳐 액화 SO2를 얻는 제 1공정과;Caustic soda solution is sprayed the first absorption tower (10) neutralization by the surface in contact with the exhaust gas fed to the SO X amount and the NO X trapping part, and SO X are all acidic sulfite soda aqueous solution to which (NaHSO 3) The A first step of separating and heating the aqueous solution, then discharging it into sulfurous acid gas, drying and compressing and cooling to obtain liquefied SO 2 ; SO2가 제거된 기체 혼합물을 촉매반응기(40)에서 산화반응시켜서 이산화질소를 만들고 제 2흡수탑(70)에서 물에 용해시켜 질산(HNO3)을 얻는 제 2공정과;A second step of oxidizing the gas mixture from which SO 2 is removed in the catalytic reactor 40 to produce nitrogen dioxide and dissolving it in water in the second absorption tower 70 to obtain nitric acid (HNO 3 ); 그리고, 제 2흡수탑(70)에서 배기되는 나머지 혼합물을 가성소다 용액을 분사하는 제 3흡수탑(80)에서 중화반응시켜 Na2CO3용액을 회수하여 결정화 하고 남은 가스를 대기로 배출하는 제 3공정으로 이루어진 배기가스 처리와 처리 부산물의 제조방법.In addition, the remaining mixture exhausted from the second absorption tower 70 is neutralized in the third absorption tower 80 injecting the caustic soda solution to recover the Na 2 CO 3 solution to crystallize and discharge the remaining gas to the atmosphere Exhaust gas treatment and process by-products consisting of three processes. 제 1 항에 있어서, 상기 제 1 공정에서 제 1중화조(10)의 중화반응은 50℃ 이하에서 반응이 일어나게 하는 것을 특징으로 하는 배기가스 처리와 처리 부산물의 제조방법.The method according to claim 1, wherein the neutralization reaction of the first neutralization tank (10) in the first step causes the reaction to occur at 50 ° C or lower. 제 1 항에 있어서, 상기 제 2 공정에서 산화반응은 기체 혼합물을 가스상태의 공기와 함께 산화조(40)에 주입하거나 촉매층을 통과시키거나 또는 50℃이상의 온도를 유지하여 반응이 일어나도록 하는 것을 특징으로 하는 배기가스 처리와 처리 부산물의 제조방법.The method of claim 1, wherein the oxidation reaction in the second process is to inject the gas mixture with the gaseous air into the oxidation tank 40, to pass through the catalyst bed or to maintain the temperature above 50 ℃ A process for producing exhaust gas treatment and by-products characterized by the above-mentioned.
KR1019990011777A 1999-04-03 1999-04-03 Method for treating waste gas and manufacturing by-product chemicals simultaneously KR20000065466A (en)

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JPH03254817A (en) * 1990-03-05 1991-11-13 Sumitomo Heavy Ind Ltd Method for treating byproduct of desulfurization and denitration apparatus
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